US20130230405A1 - Nickel base superalloy compositions being substantially free of rhenium and superalloy articles - Google Patents
Nickel base superalloy compositions being substantially free of rhenium and superalloy articles Download PDFInfo
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- US20130230405A1 US20130230405A1 US11/964,668 US96466807A US2013230405A1 US 20130230405 A1 US20130230405 A1 US 20130230405A1 US 96466807 A US96466807 A US 96466807A US 2013230405 A1 US2013230405 A1 US 2013230405A1
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- Prior art keywords
- superalloy composition
- present
- nickel base
- nickel
- base superalloy
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Classifications
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01D—NON-POSITIVE DISPLACEMENT MACHINES OR ENGINES, e.g. STEAM TURBINES
- F01D5/00—Blades; Blade-carrying members; Heating, heat-insulating, cooling or antivibration means on the blades or the members
- F01D5/12—Blades
- F01D5/14—Form or construction
- F01D5/147—Construction, i.e. structural features, e.g. of weight-saving hollow blades
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/03—Alloys based on nickel or cobalt based on nickel
- C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
- C22C19/051—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
- C22C19/057—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being less 10%
Definitions
- Embodiments disclosed herein pertain generally to nickel base superalloys and articles of manufacture comprising nickel base superalloys. Disclosed embodiments may be utilized for components disposed in hot sections of a gas turbine engine, and more particularly for use in non-creep limited applications, such as turbine nozzles and shrouds.
- Nickel-base superalloys are used extensively throughout the aeroengine in turbine blade, nozzle, and shroud applications. Aeroengine designs for improved engine performance require alloys with increasingly higher temperature capability. Although shroud and nozzle applications do not require the same level of high temperature creep resistance as blade applications, they do require similar resistance to thermal mechanical failure and environmental degradation. Superalloys are used for these demanding applications because they maintain their strength at up to 90% of their melting temperature and have excellent environmental resistance.
- SC superalloys may be divided into “four generations” based on similarities in alloy composition and performance.
- a defining characteristic of so-called “first generation” SC superalloys is the absence of the alloying element rhenium (Re).
- Re alloying element
- a representative SC nickel-base superalloy is known in the art as Rene N4 having a nominal composition of: 6.0-7.0% Co, 9.5-10.0% Cr, 1.5% Mo, 6.0% W, 4.8% Ta, 4.2% Al, 3.5% Ti, 0.5% Nb, 0.01 maximum % B, 0.2 maximum % Hf, and balance essentially Ni and C wherein C is specified as 0.01% (100 ppm) maximum.
- Mach 1 velocity cyclic oxidation Test at 2150° F. data for a Rene N4 superalloy and an AM1 superalloy are provided for comparative purposes in the accompanying Figures.
- the patent stresses that a higher “P-value” correlates with high strength in combination with stability, heat treatability, and resistance to oxidation and
- U.S. Pat. No. 6,074,602 is directed to nickel-base superalloys suitable for making single-crystal castings.
- the superalloys disclosed therein include, in weight percentages: 5-10 Cr, 5-10 Co, 0-2 Mo, 3-8 W, 3-8 Ta, 0-2 Ti, 5-7 Al, up to 6 Re, 0.08-0.2 Hf, 0.03-0.07 C, 0.003-0.006 B, 0.0-0.04 Y, the balance being nickel and incidental impurities.
- These superalloys exhibit increased temperature capability, based on stress rupture strength and low and high cycle fatigue properties, as compared to the first-generation nickel-base superalloys. Further, the superalloys exhibit better resistance to cyclic oxidation degradation and hot corrosion than first-generation superalloys.
- U.S. Pat. Nos. 5,151,249; 5,366,695; 6,007,645 and 6,966,956 are directed to third- and fourth-generation superalloys.
- third-generation superalloys are characterized by inclusion of about 6 wt % Re; fourth generation superalloys include about 6 wt % Re, as well as the alloying element Ru.
- These superalloy compositions illustrate the value of increased Re additions in terms of mechanical performance.
- First generation SC superalloys do not offer the thermal mechanical failure (TMF) resistance or the environmental resistance required in many hot section components such as turbine nozzles and shrouds. Also, first-generation SC superalloys do not offer acceptable high temperature oxidation resistance for these components.
- TMF thermal mechanical failure
- first-generation SC superalloys do not offer acceptable high temperature oxidation resistance for these components.
- the alloying element Re is the most potent solid solution strengthener known for this class of superalloys and therefore it has been used extensively as an alloying addition in SC and columnar-grained directionally solidified (DS) superalloys.
- the second-generation superalloys exhibit exceptional high temperature oxidation capability balanced with satisfactory mechanical properties.
- nickel-base superalloy compositions being substantially free of rhenium that are able to provide desired high temperature mechanical properties and oxidation resistance.
- An exemplary embodiment provides a nickel base superalloy composition including, in percentages by weight: about 5-8 Cr; about 7-8 Co; about 1.3-2.2 Mo; about 4.75-6.75 W; about 6.0-7.0 Ta; if present, up to about 0.5 Ti; about 6.0-6.4 Al; if present, up to about 1.3 Re; about 0.15-0.6 Hf; if present, from about 0.03-0.06 C; if present, up to about 0.004 B; if present, one or more rare earths selected from Y, La, and Ce up to about 0.03 total, the balance being nickel and incidental impurities.
- An exemplary embodiment provides a nickel base single-crystal article comprising a superalloy including, in percentages by weight: about 5-8 Cr; about 7-8 Co; about 1.3-2.2 Mo; about 4.75-6.75 W; about 6.0-7.0 Ta; if present, up to about 0.5 Ti; about 6.0-6.4 Al; if present, up to about 1.3 Re; about 0.15-0.6 Hf; if present, from about 0.03-0.06 C; if present, up to about 0.004 B; if present, one or more rare earths selected from Y, La, and Ce up to about 0.03 total, the balance being nickel and incidental impurities.
- An exemplary embodiment provides a gas turbine engine component cast from a nickel base superalloy composition comprising: about 5-8 Cr; about 7-8 Co; about 1.3-2.2 Mo; about 4.75-6.75 W; about 6.0-7.0 Ta; if present, up to about 0.5 Ti; about 6.0-6.4 Al; if present, up to about 1.3 Re; about 0.15-0.6 Hf; if present, from about 0.03-0.06 C; if present, up to about 0.004 B; if present, one or more rare earths selected from Y, La, and Ce up to about 0.03 total, the balance being nickel and incidental impurities.
- FIG. 1 is a graphical representation of comparative sustained-peak low cycle fatigue (SPLCF) properties.
- FIG. 2 is a graphical representation of comparative Mach 1 Velocity Cyclic Oxidation Test data at 2150° F.
- FIG. 3 is a graphical representation of comparative Mach 1 Velocity Cyclic Oxidation Test data at 2000° F.
- FIG. 4 is a graphical representation of comparative Mach 1 Velocity Cyclic Oxidation Test data at 2150° F.
- FIG. 5 is a graphical representation of creep rupture data at 2100° F./10 ksi, normalized to a second-generation nickel base superalloy having about 3 wt % Re content.
- FIG. 6 is a graphical representation of creep rupture data at 1600° F., 1800° F., 2000° F., and 2100° F., normalized to a second-generation nickel base superalloy having about 3 wt % Re.
- FIG. 7 is a graphical representation of SPLCF data at 2000° F. and 1600° F., normalized to a second-generation nickel base superalloy having about 3 wt % Re.
- FIG. 8 is a graphical representation of SPLCF data at 2000° F., normalized to a second-generation nickel base superalloy having about 3 wt % Re.
- FIG. 9 is a schematic representation of an exemplary gas turbine engine turbine blade.
- FIG. 9 depicts a component article 20 of the gas turbine engine, illustrated as a gas turbine blade 22 .
- the gas turbine blade 22 includes an airfoil 24 , and attachment 26 in the form of the dovetail to attach the gas turbine blade 22 to the turbine disc (not shown), and a laterally extending platform 28 intermediate the airfoil 24 and the attachment 26 .
- a component article 20 is substantially a single crystal. That is, the component article 20 is at least about 80% by volume, and more preferably at least about 95% by volume, a single grain with a single crystallographic orientation.
- the single-crystal structure is prepared by the directional solidification of an alloy composition by methods known to those with skill in the art.
- the component article 20 is a directionally oriented poly-crystal, in which there are at least several grains all with a commonly oriented preferred growth direction.
- alloy composition discussed herein may be employed in other gas turbine engine components such as nozzles, shrouds, and splash plates.
- Embodiments disclosed herein balance the contributions of various alloying elements to the thermal mechanical properties, creep strength, and oxidation resistance of the compositions while minimizing detrimental effects. All values are expressed as a percentage by weight unless otherwise noted.
- certain embodiments disclosed herein include at least about 5% chromium (Cr). Amounts less than about 5% may reduce the hot corrosion resistance. Amounts greater than about 8% may lead to topologically close-packed (TCP) phase instability and poor cyclic oxidation resistance.
- Cr chromium
- Certain embodiments disclosed herein include at least about 7% to about 8% Co. Lower amounts of cobalt may reduce alloy stability. Greater amounts may reduce the gamma prime solves temperature, thus impacting high temperature strength and oxidation resistance.
- Mo molybdenum
- the minimum value is sufficient to impart solid solution strengthening. Amounts exceeding the maximum may lead to surface instability. Greater amounts of Mo may also negatively impact both hot corrosion and oxidation resistance.
- Certain embodiments disclosed herein include tungsten (W) in amounts from about 4.75% to about 6.75%. Lower amounts of W may decrease strength. Higher amounts may produce instability with respect to TCP phase formation. Higher amounts may also reduce oxidation capability.
- W tungsten
- Certain embodiments disclosed herein may include tantalum (Ta) in amounts from about 6.0% to about 7.0%.
- Other embodiments may include Ta in amounts from about 6.25% to about 6.5%.
- Certain embodiments disclosed herein may include aluminum (Al) in amounts from about 6.0% to about 6.5%. Other embodiments may include from about 6.2% to about 6.5% Al.
- Titanium is a potent gamma prime hardener.
- the optional Ti addition can strengthen the gamma prime phase, thus improving creep capability.
- oxidation resistance can be adversely affected by the addition of Ti, especially at levels greater than about 0.5%.
- a superalloy composition includes substantially no Re content.
- substantially no Re content it is meant that Re additions are not nominally called for in an exemplary composition.
- compatible revert alloy i.e., used, scrap, or otherwise reclaimed, alloy
- Re may be present in amounts up to about 1.3%.
- hafnium in amounts of from about 0.15% to about 0.6%.
- Hafnium is utilized to improve the oxidation and hot corrosion resistance of coated alloys and can improve the life of an applied thermal barrier coating.
- Hafnium additions of about 0.7% can be satisfactory, but additions of greater than about 1% adversely impact stress rupture properties and the incipient melting temperature.
- Certain embodiments disclosed herein may include up to about 0.004% boron (B).
- B provides strains for low angle boundaries and enhanced acceptability limits for components having low angle grain boundaries.
- Carbon (C), if present, may be included in amounts of from about 0.03% to about 0.06%. The lower limit provides sufficient C to allow for a cleaner melting alloy and to aid in promoting corrosion resistance.
- Rare earth additions i.e., yttrium (Y), lanthanum (La), and cerium (Ce), may be optionally provided in certain embodiments in amounts up to about 0.03%. These additions may improve oxidation resistance by enhancing the retention of the protective alumina scale. Greater amounts may promote mold/metal reaction at the casting surface, increasing the component inclusion content.
- An exemplary embodiment includes a nickel base superalloy comprising, in weight percent, a nominal composition comprising: 6.0 Cr, 7.5 Co, 1.5-2.0 Mo, 6.0-6.5 W, 6.5 Ta, 0 Ti, 6.2 Al, 0 Re, 0.15 to 0.6 Hf, 0.03-0.06 C, 0.004 B, the balance being nickel and incidental impurities.
- Certain exemplary embodiments are further characterized by P-values of less than 3360, wherein the P-values are determined in accordance with the relationship provided above. In exemplary embodiments, the P-values are less than 3250.
- Re Ratio is defined herein as the ratio of wt % Re to the total of wt % W plus wt % Mo.
- the Re ratio is essentially zero (e.g., alloys 1-4, 15 and 16).
- the values for each composition are given in weight %, the balance being nickel and incidental impurities.
- a nominal composition, Re ratio, and P value is provided for Rene N5.
- Table 2 below provides another exemplary composition series, associated Re ratios, and Creep Rupture (CR) data, normalized to a second-generation (i.e. 3% Re) nickel base superalloy.
- the exemplary compositions in Table 2 provide compositions having about 1 wt % Re which are able to provide desired creep rupture strength.
- Data from Table 2 as compared to a second-generation alloy (3 wt % Re) and a first generation alloy (0 wt % Re) is presented in FIG. 8 .
- FIG. 1 illustrates the improved sustained-peak low cycle fatigue (SPLCF) properties of certain embodiments disclosed herein that are beyond that of first-generation superalloys, and more comparable to second-generation superalloys.
- SPLCF sustained-peak low cycle fatigue
- First generation SC superalloys do not offer thermal mechanical failure (TMF) resistance required in many hot section components.
- TMF thermal mechanical failure
- SPLCF is driven by a unique combination of properties, one of which is oxidation resistance. SPLCF or TMF capability is important for cooled hardware because of the temperature gradient within the part.
- FIG. 2 provides a comparative graphical representation of data showing weight loss over time during a Mach 1 Velocity Cyclic Oxidation Test at 2150° F., illustrating improved oxidation resistance for certain embodiments disclosed herein.
- FIG. 3 provides a comparative graphical representation of data showing weight loss over time during a Mach 1 Velocity Cyclic Oxidation Test at 2000° F., illustrating improved oxidation resistance for certain embodiments disclosed herein.
- FIG. 4 provides a comparative graphical representation of data showing weight loss over time during a Mach 1 Velocity Cyclic Oxidation Test at 2000° F., illustrating improved oxidation resistance for certain embodiments disclosed herein.
- FIG. 5 is a graphical representation of creep rupture data at 2100° F./10 ksi, normalized to a second-generation nickel base superalloy having about 3 wt % Re content. Certain embodiments disclosed herein compare favorably with the second-generation superalloys, and exhibit marked improvement over first-generation superalloys. It is believed that stability of the gamma prime phase, especially at temperatures in excess of 2100° F., contributes to the improved properties. In certain of the compositions disclosed herein, the volume fraction of the gamma prime phase at 2150° F. is about 46%, comparable to second-generation superalloys, and generally greater than first-generation superalloys. The relative stability of the gamma prime phase benefits the SPLCF resistance and positively affects the creep rupture properties at 2100° F.
- Creep rupture data normalized to a second-generation nickel base superalloy illustrate that embodiments disclosed herein having low Re content are more comparable to second-generation superalloys than first-generation superalloys. Normalized creep rupture data at 1600° F., 1800° F., 2000° F., and 2100° F. for alloy 5-alloy 14 (Table 1) is provided in FIG. 6 .
- FIG. 7 is a graphical representation of SPLCF data at 2000° F. and 1600° F., normalized to a second-generation nickel base superalloy having about 3 wt % Re.
- FIG. 8 is a graphical representation of SPLCF data at 2000° F., normalized to a second-generation nickel base superalloy having about 3 wt % Re.
- Superalloy compositions disclosed herein may be utilized to produce single crystal articles having temperature capability on par with articles made from second-generation superalloys.
- An article so produced may be a component for a gas turbine engine.
- Such an article may be an airfoil member for a gas turbine engine blade or vane.
- the article so produced may be a nozzle, shroud, splash plate, or other high temperature component.
- Certain exemplary embodiments disclosed herein may be especially useful when directionally solidified as hot-section components of aircraft gas turbine engines, particularly rotating blades.
- a method for producing any of the articles of manufacture disclosed herein includes preparing a nickel base single crystal superalloy element material having a chemical composition as set forth in the disclosed embodiments, from raw materials containing nickel, cobalt, chromium, molybdenum, tungsten, aluminum, tantalum, optionally titanium, substantially 0 wt % rhenium, hafnium, optionally carbon, optionally one or more of yttrium, cesium, and lanthanum.
- the superalloy element material is subjected to suitable heat treatment and suitable subsequent casting processes.
- Alternate embodiments include substituting revert superalloy material for at least a portion of the raw materials.
- embodiments nominally reciting no Re content may include up to about 1.3 wt % Re upon use of revert material.
- superalloy compositions disclosed herein provide the desired thermal mechanical properties, creep strength, and oxidation resistance with reduced Re content by balancing the contributions of compositional elements.
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- Chemical & Material Sciences (AREA)
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- General Engineering & Computer Science (AREA)
- Turbine Rotor Nozzle Sealing (AREA)
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US11/964,668 US20130230405A1 (en) | 2007-08-31 | 2007-12-26 | Nickel base superalloy compositions being substantially free of rhenium and superalloy articles |
CN200880105530.5A CN101790593A (zh) | 2007-08-31 | 2008-08-25 | 基本无铼的镍基超合金组合物及超合金制品 |
PCT/US2008/074171 WO2009032579A1 (fr) | 2007-08-31 | 2008-08-25 | Composition de superalliage au nickel sensiblement exempte de rhénium, et articles en superalliage |
EP08798597A EP2188401A1 (fr) | 2007-08-31 | 2008-08-25 | Composition de superalliage au nickel sensiblement exempte de rhénium, et articles en superalliage |
CN201410525776.5A CN104313397A (zh) | 2007-08-31 | 2008-08-25 | 基本无铼的镍基超合金组合物及超合金制品 |
JP2010523068A JP5595917B2 (ja) | 2007-08-31 | 2008-08-25 | 実質的にレニウムを含まないニッケル基超合金組成物及び超合金物品 |
CA2696939A CA2696939A1 (fr) | 2007-08-31 | 2008-08-25 | Composition de superalliage au nickel sensiblement exempte de rhenium, et articles en superalliage |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US96936007P | 2007-08-31 | 2007-08-31 | |
US11/964,668 US20130230405A1 (en) | 2007-08-31 | 2007-12-26 | Nickel base superalloy compositions being substantially free of rhenium and superalloy articles |
Publications (1)
Publication Number | Publication Date |
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US20130230405A1 true US20130230405A1 (en) | 2013-09-05 |
Family
ID=40092097
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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US11/964,668 Abandoned US20130230405A1 (en) | 2007-08-31 | 2007-12-26 | Nickel base superalloy compositions being substantially free of rhenium and superalloy articles |
Country Status (6)
Country | Link |
---|---|
US (1) | US20130230405A1 (fr) |
EP (1) | EP2188401A1 (fr) |
JP (1) | JP5595917B2 (fr) |
CN (2) | CN101790593A (fr) |
CA (1) | CA2696939A1 (fr) |
WO (1) | WO2009032579A1 (fr) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3091095A1 (fr) | 2015-05-05 | 2016-11-09 | MTU Aero Engines GmbH | Superalliage à base de nickel sans rhénium à faible densité |
US9580774B2 (en) | 2012-10-26 | 2017-02-28 | MTU Aero Engines AG | Creep-resistant, rhenium-free nickel base superalloy |
US10253396B2 (en) * | 2016-09-02 | 2019-04-09 | General Electric Company | Modified articles, coated articles, and modified alloys |
EP4273289A1 (fr) * | 2022-05-05 | 2023-11-08 | General Electric Company | Superalliages à base de nickel et composants |
Families Citing this family (11)
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EP2229462A1 (fr) * | 2007-12-26 | 2010-09-22 | General Electric Company | Compositions de superalliage à base de nickel, articles de superalliage et procédés de stabilisation de compositions de superalliage |
US20100254822A1 (en) * | 2009-03-24 | 2010-10-07 | Brian Thomas Hazel | Super oxidation and cyclic damage resistant nickel-base superalloy and articles formed therefrom |
US20100329921A1 (en) * | 2009-06-30 | 2010-12-30 | Joshua Leigh Miller | Nickel base superalloy compositions and superalloy articles |
US20110076180A1 (en) * | 2009-09-30 | 2011-03-31 | General Electric Company | Nickel-Based Superalloys and Articles |
US20110076181A1 (en) * | 2009-09-30 | 2011-03-31 | General Electric Company | Nickel-Based Superalloys and Articles |
US9850765B2 (en) | 2011-12-07 | 2017-12-26 | MTU Aero Engines AG | Rhenium-free or rhenium-reduced nickel-base superalloy |
US10378087B2 (en) * | 2015-12-09 | 2019-08-13 | General Electric Company | Nickel base super alloys and methods of making the same |
FR3072717B1 (fr) * | 2017-10-20 | 2019-10-11 | Safran | Piece de turbine en superalliage comprenant du rhenium et procede de fabrication associe |
CN108256192B (zh) * | 2018-01-10 | 2021-06-01 | 中国科学院金属研究所 | 一种金属材料基于低周疲劳的热机械疲劳寿命预测方法 |
US10577679B1 (en) | 2018-12-04 | 2020-03-03 | General Electric Company | Gamma prime strengthened nickel superalloy for additive manufacturing |
CN116045310B (zh) * | 2023-01-29 | 2024-09-06 | 中国航发沈阳发动机研究所 | 一种带除灰功能的燃烧室预旋供气装置 |
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GR80048B (en) * | 1983-12-27 | 1984-11-30 | Gen Electric | Yttrium and yttrium-silicon bearing nickel-based superalloys especially useful as comptible coatings for advanced superalloys |
GR80049B (en) * | 1983-12-27 | 1984-12-30 | Gen Electric | Nickel-based superalloys especially useful as compatible protective environmental coatings for advanced superalloys |
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2007
- 2007-12-26 US US11/964,668 patent/US20130230405A1/en not_active Abandoned
-
2008
- 2008-08-25 JP JP2010523068A patent/JP5595917B2/ja not_active Expired - Fee Related
- 2008-08-25 WO PCT/US2008/074171 patent/WO2009032579A1/fr active Application Filing
- 2008-08-25 CN CN200880105530.5A patent/CN101790593A/zh active Pending
- 2008-08-25 CN CN201410525776.5A patent/CN104313397A/zh active Pending
- 2008-08-25 CA CA2696939A patent/CA2696939A1/fr not_active Abandoned
- 2008-08-25 EP EP08798597A patent/EP2188401A1/fr not_active Withdrawn
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US3655458A (en) * | 1970-07-10 | 1972-04-11 | Federal Mogul Corp | Process for making nickel-based superalloys |
US5100484A (en) * | 1985-10-15 | 1992-03-31 | General Electric Company | Heat treatment for nickel-base superalloys |
US5011353A (en) * | 1988-12-06 | 1991-04-30 | Allied-Signal Inc. | High temperature turbine engine structure |
US5630700A (en) * | 1996-04-26 | 1997-05-20 | General Electric Company | Floating vane turbine nozzle |
US20050092398A1 (en) * | 2002-03-27 | 2005-05-05 | National Institute For Materials Science Ishikawajima-Harima Heavy Industries Co. Ltd. | Ni-base directionally solidified superalloy and ni-base single crystal superalloy |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9580774B2 (en) | 2012-10-26 | 2017-02-28 | MTU Aero Engines AG | Creep-resistant, rhenium-free nickel base superalloy |
EP3091095A1 (fr) | 2015-05-05 | 2016-11-09 | MTU Aero Engines GmbH | Superalliage à base de nickel sans rhénium à faible densité |
US10253396B2 (en) * | 2016-09-02 | 2019-04-09 | General Electric Company | Modified articles, coated articles, and modified alloys |
EP4273289A1 (fr) * | 2022-05-05 | 2023-11-08 | General Electric Company | Superalliages à base de nickel et composants |
Also Published As
Publication number | Publication date |
---|---|
JP2011514431A (ja) | 2011-05-06 |
CA2696939A1 (fr) | 2009-03-12 |
CN104313397A (zh) | 2015-01-28 |
CN101790593A (zh) | 2010-07-28 |
WO2009032579A1 (fr) | 2009-03-12 |
EP2188401A1 (fr) | 2010-05-26 |
JP5595917B2 (ja) | 2014-09-24 |
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